Functionally substituted terpolymers and tetrapolymers of {60 -olefins and process for manufacturing functional substituted copolymers

ABSTRACT

Addition terpolymers of ethylene with an Alpha -olefin and an unsaturated, functionally substituted monomer. Addition tetrapolymers of ethylene with an Alpha -olefin having 3-18 carbon atoms, a nonconjugated diene having only one polymerizable double bond, and an unsaturated, functionally substituted monomer. A process for preparing copolymers of ethylene with an unsaturated functionally substituted monomer, and optionally also with at least one of the following: an Alpha -olefin having 3-18 carbon atoms and a nonconjugated diene having only one polymerizable double bond; wherein the monomers are contacted in the presence of a vanadium compound soluble in hydrocarbons and chlorinated hydrocarbons, in which vanadium is in the oxidation state of at least +3, an organoaluminum compound, and an organic compound having at least one carbon atom substituted by three halogen atoms which can be chlorine or bromine.

United States Patent 1191 Collette et al.

1 1 May 20, 1975 i 1 FUNCTIONALLY SUBSTITUTED TERPOLYMERS ANDTETRAPOLYMERS OF a-OLEFINS AND'PROCESS FOR MANUFACTURING FUNCTIONALSUBSTITUTED COPOLYMERS [75] Inventors: John Wilfred Collette; RollandShih-Yuan Rog Fred Max Sonnenberg, all of Wilmington, Del.

[73] Assignce: E. I. du Pont de Nemours and Company, Wilmington. Del.

[22] Filed: Apr. 27, 1973 [21] Appi. No.: 355,084

Related US. Application Data [62] Division of Ser. No. 829.758, June 2,[969, Pat. No.

[52] US. Cl. 260/80.78; 260/80.6; 260/8073; 260180.75; 260l80.8

[5 1] Int. Cl. C08f 3/86; C08f i128; C08f l5/40; C08f 27/ i0 [58] Fieldof Search... 260180.78, 80.75

[56] References Cited UNITED STATES PATENTS 3,250,754 5/ l 966 Stewartzoo/80.5

3.310.531 3Il967 Natta etal. ..26o/19.s R 3.328.362 6/1967 Roberts m1;260/793 R 3,476,726 "/1969 Giannini etal. 260/89.7 N

Primary Examiner-Joseph L. Sehofer Assistant Examiner-A. L. Clingman[57] ABSTRACT presence of a vanadium compound soluble in hydrocarbonsand chlorinated hydrocarbons, in which vanadium is in the oxidationstate of at least +3, an organealuminum compound, and an organiccompound having at least one carbon atom substituted by three halogenatoms which can be chlorine or bromine.

3 Claims, No Drawings 1 2 FUNCTIONALLY SUBSTITUTED TERIOLYMERS with anaoleiin. a nonconjugated dienc. or both. by the AND TETRAPOLYMERS OFa-OLEF INS AND process of the present invention: PROCESS FORMANUFACTURING FUNCTIONAL v I. Compounds of the fonnula I SUBSTITUTEDCOPOLYMERS This is a division. of application Ser. No. 829.758, 5 4CHFCH'(CH)"X m I filed June 2. i969 now U.S.Pat. No. 3.748.316. where Xcan be one of the following groups:

2 e t OR, -NR2, -OCCF3, -C -R,-O-CCR3, -F,8r,or-C1 BACKGR UND F THINVENTION and R can be alkyl, aryl. or cycloalkyl containing 1- i 8 Thisinvention relates to a new copolymerization procarbon hydrogen? ccss andto new terpolymers and tetrapolymers having is Compwnd' of formulfunctional groups which can be obtained thereby. H. c -m y n 0.20 n

it is well known to copolymcrize certain olefinic and vinyl monomers inthe presence of free-radical generatwhere Y can be one of the followinggroups: ing initiators. Some olefinic monomers, such as propylene.isobutylene. and butene either cannot be poly- 20 0 (R1) merized at allin the presence of free-radical initiators -co p. c -N c] or can bepolymerized only to low molecular weight 2 polymers. Polymerization ofdiolefins or divinyl com- OH pounds by a free radical process leads tohighly crosslinked polymers which are 0f limited practical value. whereR can be am". an" or cycloalkyl, containing Coordination catalysts.which allow a much better 48 carbon atoms or hydrogen; R can be either Ror control of the polymerization process, often are not OR suitable foruse with monomers having functional groups containing elements otherthan carbon and hydrogen. Usually, coordination catalysts tend tocomplex with polar functional groups and such complexed (H -Z. n a 0-20catalysts either become completely deactivated or decay at a fast rate.

copoiymers of clef-mic monomers with several where 2 can be either X [asdefined in (i) above] or 3. Compounds of the formula III monomerscontaining functional groups have been re- Y [35 defined m (2) above];and

ported. Terpolymers of ethylene with propylene and Compounds of theformula w certain unsaturated acid amides, nitriles, anhydrides.

and esters have also recently been described in US.

Pat. No. 3,278,495. However, neither terpolymers of 40 OCHyCHsCH- tcu i-cu-ca IV ethylene and a-olefins with monomers containing otherfunctional groups nor tetrapolymers of ethylene with T a-olefins, dienesand functional monomers are known. when T can be hydrogen CFC" alkylCFC]a SUMMARY OF THE INVENTION Yv of a halogen- Tetrapolymers made withall the above functional Accordingly it has now been d'scovered P novelmonomers are new compositions of matter. Certain terclflslomel'icethylene random p y with polymersprepared by the process of thisinvention also fins having 3-l8 carbon atoms and unsaturated funcare newto he am They indude tel-polymers f um. lional monomers and 0fieli'apolymefs with ""i"' ene with an a-olefin and a functional monomerwhich Salad diaries having y one Polymerizabie double can be representedby one of the following formulas V bond can be readily made using acoordination catalyst through my;

based on a vanadium compound. in which the vanadium is in the oxidationstate of +3 or higher. Random distribution of the monomer units in aterpolymer or r (CH2) v tetrapolymer molecule IS often useful for goodelastic properties of the material. An aluminum aryl or alkyl or anarylor alkylaluminum chloride or bromide also is present. When thefunctional groups of the monomer contain either oxygen or nitrogen. themolar concen- 0 K OH tration of the organoaluminum compound is at least2 n equal to that of the functional monomer. Reduced vanadium isregenerated by an oxidizing agent which is preferably an organiccompound having at least one carbon atom substituted by three halogenatoms se- R Ut -(H GH: l lected from chlorine and bromine. Thecopolymerization is run in solution in an organic solvent. 9

The followingmonomers having functional groups can be copolymerized withethylene and optionally also 01a, vm I ca cu (ca i uu Ix lcn i {m x ca01- (01 5020 xl lcn i 802C] xu 9 CH CH'lCl-i l -C'l Xlll 3 (m c l xlvwhere R, R,, m and n have the same meaning as in formulas l-lV, above;these functional monomers all are derived from, and are special casesof, the broader classes of monomers represented by formulas l-lll.

DETAILED DESCRIPTION OF THE INVENTION Copolymerization of ethylene witha functionally substituted monomer optionally also with an a-olefin, anonconjugated diene, or both can be run either batchwise orcontinuously, at either atmospheric or supet-atmospheric pressure. Asolvent usually is employcd, although it is not absolutely necessary.Good solvents are aliphatic hydrocarbons such'as pentane, hexane,heptane, octane, and isooctanes; cycloaliphatic hydrocarbons, such ascyclopentane, cyclohexane, cycloheptane, and cyclooctane: andhalogenated aliphatic hydrocarbons, for example, perchloroethylene,carbon tetrachloride, methylene'chloride, and chloroform.

The reaction catalyst iscomposed ofthe i'ollowing constituents:

a. A vanadium compound in which vanadium is in an oxidation state of +3or higher; for example, VCL,

\ CIC} I l AA:

where A, A, and A, each can independently be a halogen, alkyl,haloalkyl, aryl, haloaryl; and A also can be hydrogen.

Representative halogenated compounds are, for example, chloroform,bromoforrmcarbon tetrachloride, a,a,a-trichlorotoluene,a,a,a-tribromotoluene, trichloroacetic acid, tribromoacetic acid,perchloropropylene, hexachloroacetone, ethyl trichloroacetate and ethyltribromoacetate.

Normally, at least two moles of organoaluminum compound are present foreach mole of vanadium compound. However, the preferred ratio is about10:] or

more. Organoaluminum compounds required in this process are decomposedin'the presence of monomers having active hydrogenatorns, such ascarboxylic acids or alcohols. Furthermore, they are complexed anddeactivated by oxygenand nitrogen-containing polar groups. It is,therefore, advantageous to have in the mixture a sufficient amount ofthe organoaluminum compound to at least compensate for its decompositionor deactivation. An excess of the organoaluminum compound is notharmfuhand molar ratios of alumi- -nurnto vanadium compounds as high as200:1 or more can be present in the catalyst.

The halogenated compound DCL; acts as a catalyst reactivator and it canbe present. in a large excess, for instance, in an amount'of l0 molesper mole of vanadium compound. l-loweyer, the amount of the reactivatorshould be kept'within the range of about 0.0l-l mole per mole of theorganoaluminum compound present in solution. Below the lower limit'thereactivation of the vanadium catalyst-is not quite efficient, whileabove the upper limit there is a risk that polymerization may proceedbyan undesirable ionic mechanism. The

vanadium compound is present in catalytic amounts only, for example,0.00005-0.00$ mole per mole of total unsaturated monomers.

The practical concentration ranges of the essential compounds in thepresent copolymerization process are tabulated below:

equul to vunudium cuutlyst concentration Polymerization is run in theabsence of moisture in an inert atmosphere. for example in drynitrogen.and at a temperature of to lC The preferred temperature range is 0-65C.Below 0C. it is both inconvenient and expensive to remove heat evolvedduring the polymerization. Above about 65C. the molecular weight of thecopolymer product can fall below a desirable value. it is usuallyconvenient to carry out the copolymerization at atmospheric pressure,but reasons of economy of time or, equipment may sometimes favor closedsystem polymerizations at autogenous pressures or higher. It is usuallypossible, for example, to increase the monomer concentration in solutionin a ciosed system'. and a smaller reactontherefore, can be used than atatmospheric pressure. When polymerization is run in a closed system.pressures up to about 10,000 psig. can be used. but it is not practicalto exceed a pressure of about 5000 psig.

Although the process of the present invention is susceptible to changesand variations without departing from the spirit of the inventiveconcept. a typical batchwise atmospheric pressure copolymerizationinvolves the following steps: ethylene. and optionally a comonomera-olefin, are dissolved in an appropriatesolvent such asperchloroethylene. and an alkylaluminum compound is added. Thisisfollowed by addition of an unsaturated functional monomer, optionally adiene, then a catalyst reactivator and finally, a vanadium compound. Thesolution is'stirred for about minutes, while ethylene and any gaseousmonomers are continuously swept through it. The polymerization isstopped by destroying the catalyst system, for example by adding analcohol. The reactiontime insome cases may be as short asl minute, whilein other cases a period of 2 hours or more maybe requiredto-obtainsatisfactory yields of the copolymer. g

The process of the present invention can also be operated in acontinuous manner. it often is desirable in such a case to increase thereaction pressure in order to reduce the residence-time. Thereactoreffluent is continuously removed.- a

The product copolymer canbe isolated'by several known techniques, but itis preferred to precipitate it with a nonsolvent such as methanol and towash it. The functional groups of a crude copolymer often retainresidual aluminum compounds. and, sincea copolymer containing residualaluminum is unsuitable for most applications. removal of any aluminumcompounds present is advisable. Where acopolymer is precipitated fromsolution with an alcohol, it usually is sufficiently free from aluminum.but when the copolymer contains carboxyiic groups. it may be necessaryto remove the last traces of aluminum compounds. for example by atreatment with trifiuoroacetic acid. When other isolation methods areused. for example evaporation or phase decantation. it is practical toremove residual aluminum compounds by washing the copolymer solutionwith a large excess of a dilute acid. such as sulfuric, hydrochloric, oracetic acid and to remove the acid b washing with water.

Alpha-olefins which can be used as comonomers in the process of thepresent invention can be either straight-chain or branched.Representative a-olefins include propylene, butene. pentene, hexene.heptcne. deeene and octadecene. Propylene is the preferred a-ololln.Noneoniugstcd dienos which have only one polymerlzable double bond canbe present in addition to a-olefin comonomers. These includel,4-hexadiene, S-methylene-Z-norbomene, S-(2-butenyl)-2- norbornene.dicyclope'ntadiene, S-ethylidene-Z- norbornene.ll'ethyl-lJl-tridecadiene, and i,5- heptadiene'.

The unsaturated functional comonomers can have active hydrogen atoms,provided at least a'stoichiometric amount of aluminum alltyl oralkylaluminum halide also is present to preventcatalyst deactivation.Generally. the farther'is' the functional group removed from thedoublebond, the easier and more complete is the copolymerization of thefunctional comonomer. Typical compounds of the group defined by FormulaI include 4-pentene-l-ol, 5-hexene-l-ol.' S-hexene-l-ol.IO-undecenel-ol. 4-pentenyl methyl ether, 5 hexenyl methyl ether.S-hexenyl diethylamine,6-heptenyl methylethylamine, 4-pentenyltrifluoroacetate, 6-heptenyl trifluoroacetate, 4-pent enyl methylketone. S-hexenyl methyl'ke tone, 6 heptenyl; vinyl ketone. IO-undecenylchloride. 6-heptenylychloride and 4-pentenylacetate. When theunsaturated functional monomer is a member of the groupdefined byformulall, it can be, for example, one of the following compounds:acrylic acid, methacrylic acid.vinylacetic acid, IO-undecenoic acid,allylacetic acid, methyl acrylate, ethyl acrylate, propyl acrylate,methyl methacrylate, ethyl. methacrylate, butyl lO-undecenat'e, .ethylvinylacetate, propyl vinylacetate, methyl allylacetate,butyl-allylacetate, N,N- dimethylacrylamidqg acrylamide, N,N-diethylvinylacetamide, acrylonitrile, methacrylonitrile. 2- allylphenol,2-methoxy-4-allylphenol, allylsulfonyl chloride and5-norbornene-2-sulfonyl chloride. The unsaturated functional monomer canalso be a 2- norbornene derivative, as shown in Formula lll. lt'thus canbe, for example, :2-norbornene-5-acetic acid, 2 -'n0rbor'ne'ne5-propionamide, 2-norborne'ne-5- methanol, 2-norbomene-5-ethyl methylltetone. 2-norbornene 5-acetonitrile, or ethyl Z-norbornene- S-acetateMonomers having structures represented by formula .lV include. forexample, 8-phenoxy-l .6- octadiene; 9-(2'-hydroxy)phenoxy-l,o-octadiene;8(4- '-chloro )phenoxy-l ,6-octadiene; 8-(4-methylphenoxy-l,6-octadiene; and 8-(4'-methoxy)phenoxy- 1.6-octadiene. Allthese compounds are known in the art.

Although the proportions of comomers can be varied, it is preferred tomaintain the amount of a-olefm (when present) at such a level that itwill constitute 5-7$ weight percent of the product copolymer. preferablyabout 20-60 weight percent. Functional unsaturated monomer is present insuch an amount that it will constitue 0.l-l0 mole percent of theproduct. When a nonconjugated diene is used in addition to ethylene andoptionally a-olefin, it generally is employed at a level which will give0.1- mole percent diene component in the final copolymer. The amount ofethylene can be varied within rather broad limits, so long as the aboveproportions are maintained.

The novel copolymers of the present invention have desirable physicaland chemical properties which make them useful for a number ofapplications. Thus, for example, the solubility and dispersibility of anolefinic polymer are modified by the presence of functional groups. Acopolymer having functional groups is more compatible with polarsolvents than a hydrocarbon polymer. Carboxyl groups impart goodabrasion resistance, allow formation of stable latices, and. improveadhesion. Hydroxyl groups provide active sites which allow crosslinkingand/or chain extension, for instance with polyisocyanates. Otherfunctional groups, such as amino groups, improve dyeability of acopolymer. These new terpolymers and tetrapolymersare veryuseful inadhesives, especially when a'nonpolar material must be bonded to a polarsubstrate (e.g., when bondin g elastomer stocks to tire cords).

This invention will be better understood if reference is made to thefollowing examples of some specific embodiments thereof, where allparts, proportions and percentages are by weight,-unless otherwiseindicated.

EXAMPLES General Copolymerization Procedure forethylene/propylenelfunctional monomer terpolymers Batch polymerizationsare carried out at atmospheric pressure in an oven-dried 3-neckedlOOO-ml. flask equipped with a serum cap, a stirrer and a thermometer.The flask is swept with nitrogen and-filledto the 500 ml. mark withperchloroethylene at about C. Ethylene and propylene are first sweptthrough the solvent for 10 minutes at the rate of l l./minute and-2l./minute, respectively.

in a typical experiment, while ethylene and propylene are continuouslyintroduced'at the above rates, 5 ml. of a 4M solution of diethylaluminumchloride (0.02 mole) in perchloroethylene is added throughthe serum cap,followed, in turn, by a solution of 0.01 mole of unsaturated functionalmonomer in i5 ml. of perchloroethylene and l ml. of a l.0M solution ofhexachloropropylene (0.001 mole) in perchloroethylene.- The temperatureis adjusted to C. and 1 ml. of a 0.lM solution of VCl inperchloroethylene (0.001 mole) is added.

The temperature is maintained at 20-30C., cooling the flask in an icebath, as necessary. After 30 minutes.

from addition of VCL, polymerization is terminated by 8 to precipitatethe polymer; the liquid is subsequently decanted. Another 500 ml. ofmethanol is used to wash the polymer. The isolated polymer is dried at90C. for at least 3 hours in a vacuum oven.

When the copolymer contains carboxylic groups, the coplymer solution canbe treated with trifluoroacetic acid (TFAA) to remove last traces of thecatalyst. The solution (250 ml.) is mixed with 30 ml. of TFAA andallowed to stand overnight. The solid catalyst residues are filtered;and the filtrate is treated with l0 ml. of TFAA and filteredimmediately. The filtrate is concentrated in a rotary vacuum evaporatorand the solution washed three times with lOO ml. of water. The organiclayer is further concentrated to about lOO ml. and added dropwise to 500mi. of vigorously stirred acetone. The precipitated polymer is decantedand dried j in a vacuum oven for at least 3 hours at 90C.

The results of experiments l-l 0 run both with and withouthexachloropropylene (HCP) (as catalyst reac- .norbornene Controlexperiments. outside the of this invention. "In this experiment. 0.02mole of ethylaluminum dichloride is used.

General Copolymerization Procedure for ethylene/propylene] l ,4-hexadiene/functional tetrapolymers The procedure described above for thepreparation of terpolymers is used with slight modifications. Ethyleneand propylene are introduced into perchloroethylene at -5C. at the rateof L5 l./min. The amount of diethylaluminum chloride is increased to 25ml. (0.l0 mole) and the amount of functional monomer to 0.05 mole.l,4-Hexadiene, 12 ml. (0.10 mole) is added through the septum. Theamount of 0.1M VCl is 3 ml. (0 .0003 mole), and 3 ml. of l.0M (0.0003mole) hexachloropropylene is added at -5C. The tetrapolymer is recoveredby precipitation with 2 liters of methanol and washed, with 2 liters ofmethanol. The copolymer is vacuum oven-dried overnight at C. The resultsare presented in Table III.

TABLE III -Continued Incorpo- Coration by Expolymer Wt. of ampla ylold',monomer in saturation No. Functional Monomer grams copolymer moles/kg. 7I t v p 13 I 40.9 determined 04 'cn co u Not 14 c 2). 6 31- dttll'rnlnod' 0.75

"@QW; 12.5 1.8 0.14 17 "2' ',"z 2' 46.1 0.2 0.68

" strong C-O band'avldant in IR spectrum 0.15 mole of rllathylalumlnurnchloride used Adhesion testing of Functional Tctrapolymers Hard" KaolinClay: Supcrex" Clay. (J. M. Huber Corp.. New York) is an air-floatedhard" kaolin type characterized by the following equivalent analysis:44-46 percent silica. 37.5-39.5 percent alumina. 1.5-2 percent ironoxide. and 1-2 percent titanium dioxide by weight. the ignition lossbeing l3.9-l4.2 percent by weight. This analysis does not mean that theclay necessarily contains silica or alumina. The moisture content(maximum) is 1 percent by weight. The pH (in water) is about 4.5-5.5.This clay hasa specific gravity of 2.60. a 325-mesh screen residue of0.l7 percent by weight. and the following particle size distribution (byweight):

u. 0.l percent; 540p, 2.8 percent; 4-5 4, percent; 3-4 p, 2.3 percent;2-3 p, 3.4 percent; 1-2 p, 9.0 percent; 0.5-l p, l0.0 percent; 0-O.51.1., 61.9 percent.

Adhesion of ethylenc/propylene/propylene/l,4-hexadiene/functionalmonomer. tetrapolymers towards Suprex Clay is determined. in thefollowingmanner:

The tetrapolymer (20 grams) and Suprex Clay (24 grams) are compounded ona rubbcr'mill. The compounded polymer is loaded cold into a l inch X 5inch slab mold and heated at 100C. for 3 minutes. The specimen isallowed to cool. unloaded. and the tensile strength at break T, isdetermined at 25C. on an Instron machine in accordance with ASTM MethodD- The results are presented in Table lV. below:

following formula (co t:

where n is an integer-within the range 0-20 and Z is a functional groupselected from the following: NH,,

40:11, -CNH2, and -CN.

2. A copolymer of claim 1, where the functional monomer isZ-aminomethyl-S-norbomene.

3. A copolymer of claim 1, where the functional monomer isS-norbornene-Z-acetic acid.

I i i i i As a aallulitm olll.l g. ol'tetrapolymer in I00 ml. ofywrehkvroethylene "tetrapolymer Il' lltlt. by a continuous process "aprior art terpolymer having 0.. mole/kg. umuituration. and containingthe following monomer unit composit'mn: ethylene. 52. l; propylene, -l-t.0; lgz ht'llldlt'flQ, 3.). It in mode In perehhvroethylene in thepresence of a nmnlmatmn catalyst formed by In-mixing rliiurhutylalumilmmchloride aml VtX'h. 'lhc MKIIIC) t'm'oslt tMl l l-lllll an about 40.

1. AN ADDITION COPOLYMER OF (1) ETHYLENE, (2) PROPYLENE, (3)NONCONJUGATED DIENE, AND (4) AN UNSATURATED FUNCTIONAL MONOMER FROM THEGROUP REPRESENTED BY THE FOLLOWING FORMULA
 2. A copolymer of claim 1,where the functional monomer is 2-aminomethyl-5-norbornene.
 3. Acopolymer of claim 1, where the functional monomer is5-norbornene-2-acetic acid.